Denaturant



g pass. There are,,however' tmedium The e s 1 as chemicaltreatment unitil, finally; alcohokhaa been b ei fl" '1 r so natured'fmaterials. l

Patented Feb. 2'1, 1940 TED STATES PATENT OFFICE BENATURANT No Drawing: Application Eecember 18, 1937,

Serial N0. 180,583

screams. (e1. 202-77) 7 This invention relates to denaturants and more particularly to denatured alcohols and the method of denaturing them.

Many proposals have been made in the'past 5 for the use of various materials whichQwhen mixed with a. substance such as an alcohol, or ester, completely change-its taste or odor or both so that it cannot be diverted from its intended use or can readily be identified or both. For ex l0 ample, this procedure has been applied to methanol to avoid'its being taken internally, as well as to ethanol and other alcohols which might otherwise be diverted from their-intendedbommercial use to that of a beverage. Similarly,

substances such as ethyl acetate,and other esters, which might fairly easily be otherwise converted to alcohols and thus diverted from their intended use, have likewise beenjde'nature'd. {Upon chemical treatment of such esters, the denaturant has at} been intended to carry overjtofthe alcohol and cause it to beunpotable.

Materials which have been i 5r0posed as denaturants before have lhadone or more characteristicslwhich adaptthemffor denaturing purwa i hMe ea ende fe wh 1 sufiicient degre so that a denatura anaemia "h Y i e merit of the denaturedined'iurn with or iollowedby various distillation steipfsand further relatively pure Itis an Qbjectof themes? inv nt on. to

.- come the:{disadvantage oi otlieprior it and to" provide a new, andimproved denatur g t andde t It is a furtherrobject,

, e ll'eyi for l denaturant is'desired 1:01 ntify am 1e," as"methyl 'alc'o i medint an q iet addition to jdenaturlng ethyl 'est'eifsflsuch as ethyl acetate mentioned'before, the denaturants of he pr entinvention, to provide a denatured ethyl -alcohol, which 111E957 sesses a distinctive but unobjectionable odor, and- 'a taste which renders ,the ;.ethyl' alcohol unpo-- I as table. up, p

Other objects aud'advantages of the present invention will be apparent by reference to the "following specification in which the preferred embodiments and detailsare set forth.

, According to the present invention a denatured 5 material from which it is extremely difficult if not impossible to remove the denaturant is prepared by mixing 'with a liquid material such as gasoline, an ester such as ethyl acetate, an alcohol, including such alcohols as methyl, ethyl, and w .propyl, and the like, relatively small quantities of an unsaturated aliphatic alcohol containing only the elements carbon, hydrogen, and oxygen, boiling in the range of from 100 to 200 C. and having the general formula R1R2CHOH in which 35 R1 and R2 may be hydrogen or acyclic or iso cyclic hydrocarbon radicles.

, The denaturants of this invention are gnerally applicable for treatment of any normally liquid material which it isdesired to denature although, preferably, the qmaterial to be denatured should have a boiling point in the range of C. to 250 C. From a material having a boiling p'ointin this-range itwill be" found exdenaturant My denaturants are also adaptedto a'nd effective in denaturingand distinguishing motor fuels rorn one ,anotherin cases, ior example, where it Q V etsesarateind dum 3 supplies or s ocks o gasoline. Specifically, my

denaturants'i are'jlhighly-zefiectivc'e v as a means of asoline; A wide range-of-nalcohols may also be successthe range aboveiiidicate should be onewhich-ymight be fairly easily trans- -5 Thus, for example, in

ojhols possess odor and taste. Both the odor and the taste persist in spite of drastic treatment utilized for their removal.

The following examples illustrate proportions of various materials which may be utilized as denaturants. It will be noted that small quantitles only of the denaturant are necessary for denaturing purposes and that the material remaining after treatment for denaturant removal possesses an undesirable taste and a distinctive odor.

Example 1 200 cc. of denatured alcohol, prepared by adding volumes of ethyl ethynyl carbinol.

(CH3.C JHz.CH(OH) .CECH, B.P. 122125 C.) v

to 100 volumes of pure 95% ethanol, was diluted with 600 cc. of saturated salt solution and 200 cc. of water. The resulting solution was clear. It was shaken with 50 cc. of mineral oil for 3 minutes and allowed to stand over night. The water layer was shaken for 3 minutes with a 40 cc. portion of mineral oil and allowed to stand 1 hour. The water layer from the second extraction was shaken with g. of activated carbon for 30 minutes and filtered. The filtrate was then given a similar treatment with a second 10 g. portion of activated carbon. The filtrate from the second carbon treatment was then distilled at a reflux ratio of 10:1 and a draw-off rate of 1 cc. per minute using a fractionating column of approximately theoretical plates. 176 cc. of distillate was collected. The distillate had the odor and taste of the denaturant and was unpotable.

Example 2 'A denatured alcohol, prepared by adding volumes of isopropyl ethynyl carbinol (CH3.CH(CH3) .CH(OH) .C5CH,

' B.P. 133-133.5, C.)

to 100 volumes of pure 95% ethanol, was treated by the procedure of Example 1. The distillate had the odor and taste of the denaturant and was unpotable.

Example 3 An unpotable alcohol was prepared by adding 5 volumes of methallyl alcohol (CH2ZC(CH3).CH2.0H, BI. 114.5 C.)

to 100 volumes of pure 95% ethyl alcohol.

Example 4 A denatured ethyl propionate was prepared by adding 2 volumes of methallyl alcohol to 100 volumes of pure ethyl propionate.

Example 5 A denatured ethyl acetate was prepared by adding 2 volumes of isopropyl ethynyl carbinol to 100 volumes of 85% ethyl acetate.

Example 6 denaturing materials which possess stronger and more disagreeable odors than the denaturants of the present invention as a method of distinguishing the denatured alcohol utilized from other denatured alcohols or for other reasons. The material of the present invention is miscible, however, with anything, generally speaking, with which ethyl alcohol is miscible and may, therefore, be utilized in conjunction with other denaturing materials generally, such as illustrated by the following additional examples which show representative, preferred mixtures.

) Example 7 An unpotable alcohol was prepared by adding to 100 parts by volume of 95% ethyl alcohol, two parts methyl isobutyl ketone, three parts of methallyl alcohol, one part of the sulfur-containing residues obtained in the refining of petroleum and known under the name of Agdite, and one part of gasoline.

Example 8 An unpotable alcohol was prepared by adding to 100 parts by volume of 95% ethyl alcohol two parts of isopropyl ethynyl carbinol, four parts of a mixture of primary and secondary aliphatic higher iso alcohols and higher branched chain ketones (known under the name of Denol), and one part of the liquid denaturant described and claimed in my copending application S. N. 143,295, comprising a mixture of higher branched chain ketones and saturated and unsaturated hy-. drocarbons.

Example 9 An'unpotable alcohol of undesirable taste and distinctive odor may be prepared by adding to 100 parts by volume of 95% ethyl alcohol, three parts of isopropyl ethynyl carbinol, four parts of the mixture of pyroligneous bodies, free from methanol, produced by the destructive distillation of wood, and one part of gasoline.

Although the several examples illustrate the use of a variety of unsaturated alcohols according to this invention, other alcohols may equally as well be substituted therefor, such for example, as: 1-butynol-3; 1-butenol-4; 2-pentenol- 4; 2-methyl-2-pentenol-4; 1-hexenol-5; 1,6- heptadienoli; 2-methyl-6-heptenol-4, and the like.

The proportions utilized according to the present invention may vary from a very small quantity, such as one-tenth of one per cent, up to ten "per cent by volume or more of the alcohol, or

'but a single denaturant has been illustrated as used at one time, it will be understood that mixtures of my denaturants may equally as well be utilized.

A great advantage of the present denaturant resides in the fact that it does not render the denatured material commercially and scientifically undesirable inasmuch as the character 01 the denatured material is not changed by the incorporation of my denaturant.

Various changes may be made in the present invention without departing therefrom or sacrificing any of the advantages thereof.

I claim:

1. A denatured ethyl alcohol consisting of ethyl alcohol and from 0.1% to 5% by volume or 3. A denatured ethyl alcohol consisting of ethyl alcohol and from 0.1% to 5% by volume of isopropyl ethynyl carblnol.

4. A denatured ethyl alcohol consisting of ethyl alcohol and from 0.1% to 5% by volume of methyllyl alcohol.

JOHN C. WOODHOUSE. 

